CN1239331A - Cathode active material for alkaline storage battery and cathode using the same - Google Patents
Cathode active material for alkaline storage battery and cathode using the same Download PDFInfo
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- CN1239331A CN1239331A CN99101360A CN99101360A CN1239331A CN 1239331 A CN1239331 A CN 1239331A CN 99101360 A CN99101360 A CN 99101360A CN 99101360 A CN99101360 A CN 99101360A CN 1239331 A CN1239331 A CN 1239331A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention discloses a cathode active material for an alkaline storage battery, which has a high energy density and a high cycle stability. The cathode active material includes particles of a solid solution or eutectic mixture nickel oxide, which has a crystal structure of beta-Ni(OH)2 and contains at least Mn, where Mn has a mean valence of not less than 3.3, and a coating layer of a solid solution or eutectic mixture cobalt oxide formed on the surface of the particles, which contains at least one element of Ni and Mn.
Description
The present invention relates to be used for the active material of cathode of high power capacity alkaline battery, this material mainly is made up of nickeliferous metal oxide as the major metal element, also relates to the negative electrode that uses such active material.
Along with the progress of recent semiconductor technology, the development of miniaturization, electronic equipment in light weight, multi-functional (as mobile phone, notebook computer etc.) is also being carried out rapidly.Therefore press for miniaturization, lightweight alkaline battery, as the energy of this class hand portable equipment.
General with the active material of nickel oxide (NiOOH) as the alkaline battery negative electrode.The porous substrate of the three-dimensional foaming nickel of highly porous (95%) has been substituted sintering substrate commonly used.Adopt the electrode (foaming metal electrode) (United States Patent (USP) 4,251,603) that obtains by with the closely knit nickel porous substrate of inserting foaming of nickel oxide powder in the commercial Application always.This has improved the energy density of nickel cathode significantly.
A kind of important technology of the nickel cathode of high-energy-density that provides has improved the production active material, i.e. the method for nickel oxide powder.The method of production nickel oxide powder commonly used is to make alkaline aqueous solution, and for example the reactant aqueous solution of sodium hydroxide solution and nickel salt is settled out nickel hydroxide.Sediment behind the timeliness grown crystal, mechanical crushing nickel hydroxide crystal.This method requires complicated process, and the nickel hydroxide powder that obtains has unfixed shape.So just be difficult to provide the electrode of high packed density.
Disclose described in the flat 4-80513 as Japanese unexamined patent, proposed improved production method, it repeats to make ammonia and nickel salt aqueous solution reaction to form nickel-ammonium complex, and makes alkali and the reaction of this complex produce the process of nickel hydroxide, thereby makes the nickel hydroxide growth.Be that this method is deposited on the nickel hydroxide of existence nickel hydroxide.This method can generate nickel oxide continuously, and reduces production costs.The torispherical oxide that produces can reach high density and fill.
Thus obtained nickel oxide active material is to have grown into the high density granular of particle diameter up to tens microns.This has reduced the electron conduction of active material itself, and has therefore reduced electrode charging and discharging efficiency.Proposed some specific aim measures, for example, added metallic cobalt, cobalt oxide or metallic nickel, or in active material, add other metal except that cobalt or nickel, formed solid solution, improved charging and discharging efficiency with the compensate for electronic conductance.
As at Power Sources 12, described in the p203 (1988), the known example that joins in the crystal nickel oxide with the metallic element that improves charging and discharging efficiency is Cd and Co.But, require no cadmium cell from environmental.Proposed to add Zn and added three kinds of elements, Co, Zn and Ba replace cadmium (United States Patent (USP) 5,366,831).People have known the metallic element that in nickel oxide adding is different and formed solid solution, and are to reach the technology of high charge and discharging efficiency, for example disclosed in the open 51-122737 of Japanese unexamined patent.
The improvement of the grain shape of underlying structure, active material, the composition of active material and additive has obviously improved the energy density of negative electrode.The energy density of negative electrode has reached about 600mAh/cc in the practical application.But, as mentioned above, more and more need to improve the energy density of the energy that is applied to the miniaturization hand portable equipment.Another direction that improves the energy density of battery is to improve the structure of anode and negative electrode, electrolyte, dividing plate and battery.
The actual metal hydride of high-energy-density that uses replaces cadmium anode (Power Sources 12, p393 (1988)) commonly used the volume energy density of anode to be brought up to the twice that is at least the negative electrode energy density.This class technological progress is filled as the high density that forms thin film dividing plate or electrode material, has all significantly improved energy density, but has reached the limit basically.
The effective method that further improves energy density is the energy density that improves negative electrode, because negative electrode has occupied nearly half battery volume.
The packed density that has some to increase electrode materials is with the method for the energy density that improves negative electrode; For example, improve the tap density of active material particle, reduce the quantity of additive, and reduce the amount of metal that is included in the foaming nickel substrate.But these methods have reached the limit basically.Therefore, need improve reactive metal itself from improving reactivity and order of reaction angle.
Being commonly used for the nickel oxide of active material of cathode, is β-Ni (OH) in the time of in being filled into electrode basement
2(oxides, divalent) structure.It is said β-Ni (OH)
2By charging-exoelectrical reaction, can exchange an electronics and reversibly be converted into β-NiOOH (trivalent).β-the NiOOH that is in charging back state has excessive charge and is oxidized to highly oxidized γ-NiOOH structure (valence mumber: 3.5-3.8).γ-NiOOH is the irreversible stoichiometry material (J.Power Sources 8, p229 (1982)) with disordered crystal structure.
This γ-NiOOH is the electrochemistry inertia, and the result produces voltage decline and capacity reduces.γ-the interfloor distance of NiOOH broad has enlarged the volume of electrode, thereby causes many problems, for example makes the loose contact of active material and conductive agent or substrate, discharges active material and suck hydrone from substrate electrolyte is become dry.Therefore require to interfere the generation of γ-NiOOH.
Utilize high-order oxide γ-NiOOH in order to obtain to comprise the high-energy-density active material of nickel oxide, to the particularly important is as main material.A kind of material that proposes has structure (United States Patent (USP) 5,348,822 and 5 that are similar to α-type hydroxide, 569,562), it is by using another kind of metallic element, replace part Ni as Mn (III), Al (III) or Fe (III), and anion and hydrone are in interlayer and obtain.Think that this oxide has the high-order oxide that is similar to γ-NiOOH structure by charging and discharge, can reversibly being converted into.But this oxide has wide interfloor distance and low-density (real density), makes high density fill difficulty, and therefore this oxide is impracticable.
The inventor notices to have β-type crystal structure in inserting electrode process, and can the reversible active material that is converted into the γ-NiOOH of high-order oxide by charging and discharge.The inventor proposes, and for reaching charging and the exoelectrical reaction that has more than an electron exchange, can add another kind of metallic element, improves nickel oxide.Also proposed to comprise the composition of Mn, be used for being added to the metallic element (Japanese unexamined patent discloses flat 9-115543) of nickel oxide as key component.Disclosed as the document, Mn is added to mobility and the electron conduction that has strengthened proton in the nickel oxide, thereby has improved its utilance.
The solid solution nickel oxide that has proposed wherein to have added Mn among clear 51-122737, the flat 4-179056 peace 5-41212 is disclosed in Japanese unexamined patent.The inventor also notices the solid solution nickel oxide that adds Mn.The inventor has found that this solid solution nickel oxide is easy to charging and is oxidized to γ mutually by the valence mumber of the Mn that regulate to add, and discharge reaches and has the order reactive that is not less than 1.2 valence mumbers.The inventor also proposes synthetic such solid solution nickel oxide to obtain highdensity method.
As mentioned above, solid solution nickel oxide or eutectic mixture nickel oxide that a kind of method of proposition will wherein add Mn are used as active material of cathode, to improve charging and the discharging efficiency and the order of reaction.But in the material of proposition, γ-NiOOH produces during charging normal, and it can reversibly charge and discharge.Therefore the expansion of the active material in the electrode and contraction can damage the conductive network of cobalt compound.Compare with the conventional nickel oxide that wherein charges with discharge is undertaken by an about electron exchange, the generation that this will interfere the γ phase causes lower cyclical stability.
Therefore, the objective of the invention is by γ mutually being used to charge effectively and exoelectrical reaction obtains obviously high energy density, and the active material of cathode that is provided for having the alkaline battery of good cycle life characteristics.
The invention provides the active material of cathode that is used for alkaline battery, it comprises solid solution nickel oxide or eutectic mixture nickel oxide particle, has β-Ni (OH)
2Structure, and contain Mn at least, be not less than 3.3 at the average valence mumber of this Mn, be formed with the coating of cobalt oxide solid solution or eutectic mixture at particle surface, it contains at least a element among Ni and the Mn.
Requirement the content of at least a element Ni and Mn described in the coating be not less than all metallic elements that comprise in the coating molal quantity 0.5%, be not more than 20%, be preferably in and be not less than 0.5% (mole) to the scope that is not more than 10% (mole).
Requiring the content of above-mentioned coating, is benchmark with hydroxide, is not less than 1% (mole) of nickel oxide but is not more than 20% (mole).
Also preferred cathode material is sphere or torispherical powder, and its tap density is not less than 1.7g/cc.
The present invention also provides the negative electrode that is used for alkaline battery that comprises top active material.
Preferred negative electrode also comprises yttria particles.
Proposed novel features of the present invention in the following claims, and, can understand the present invention better by the detailed description of carrying out below in conjunction with accompanying drawing.
Fig. 1 is to use in the Ni-metal hydride accumulator of the active material of cathode in the embodiment of the invention, the graph of a relation between charge-discharge cycles number of times and the active material utilization.
Fig. 2 is to use in the Ni-metal hydride accumulator of active material of different Ni contents coating, the graph of a relation between charge-discharge cycles number of times and the active material utilization.
The inventor finds to contain at least Mn under solid solution state or eutectic mixture state, and Mn's is average Valence mumber is not less than in 3.3 the nickel oxide, and charging-exoelectrical reaction has two electron exchange at least when carrying out. Although extremely The present also fails the mechanism that it is detailed is described, but this oxide is recharged the γ phase that is oxidizing to higher oxidation state, should Be easy to mutually discharge. This ascribes this fact to, namely adds the Mn that valence mumber is different from Ni in nickel oxide, carries The mobility of high proton and the electronic conductivity in nickel oxide. This oxide has β-Ni (OH)2Structure, It has high density in discharge condition, thereby has good filling characteristic, can obtain the moon of high-energy-density The utmost point.
In the active material of the present invention, the cobalt oxide coating comprises at least a element among Ni and the Mn. Ni and/ Or Mn has strengthened the physics and chemistry stability of cobalt oxide. Think and so effectively prevented coating owing to repeat The dissolving of charging and discharging circulation, or particle is because the physics breaking-up of expanding and shrinking. Such arrangement makes oxidation The cobalt coating can keep conductive network in long-time charging and discharging circulation, thereby keeps improving the chemical material utilization The effect of rate.
The content of at least a element is not less than all gold in the coating in the Ni that comprises in the cobalt oxide coating and Mn Belong to the element molal quantity 0.5% the time, above-mentioned effect is particularly remarkable. Content greater than 20% (mole) can slightly reduce Conductance may cause reducing the order of reaction. Therefore preferred this content is not more than 20% (mole).
If the content of at least a element surpasses 10% (mole) among Ni and the Mn, then can disturb crystallization, make shape The particle that becomes becomes huge. Therefore, require content better (to rub being not less than 0.5% (mole) and being not more than 10% That) scope.
Being coated on the cobalt oxide amount on the nickel oxide, take hydroxide as benchmark, better is to be not less than nickel oxide heavily 1% (weight) of amount also is not more than the scope of 20% (weight).
Amount less than 1% (weight) can stop cobalt oxide fully as the function of conductive network, can reduce the discharge effect Rate. On the other hand, the amount greater than 20% (weight) has increased production cost, and can disturb crystallization, makes formation Particle huge. Therefore, the cobalt oxide amount exceeds and above-mentionedly is not less than 1% (weight) and is not more than 20% (weight) Scope the time, have obvious shortcoming.
Add in the use yittrium oxide in the negative electrode of the active material of face and can obviously improve charge efficiency under the high temperature. For making negative electrode that high-energy-density be arranged, the advantageous embodiment order of reaction, and the packed density that makes electrode is at least with commonly used The packed density of electrode equates. For the packed density that makes electrode equates with common electrode at least, active material Particle should be sphere or the torispherical powder that tap density is not less than 1.7g/cc.
Paragraph is below described the present invention in more detail with reference example.
Embodiment 1
The method of synthesizing activity material is at first described.This method provides and has contained 2.16 mol NiSO
4With 0.24 mol MnSO
4The aqueous solution, contain the aqueous solution of 5.52 mol NaOH and contain 4.8 mol NH
3The aqueous solution, and continuously these aqueous solution inputs are remained in 40 ℃ the reactor.Regulate the charging rate of each aqueous solution, make the scope of the pH of the mixed solution in the reactor at 11.5-12.5.Simultaneously, to feed gaseous state Ar in the solution of flow in reactor of 800 ml/min continuously, make the oxygen concentration that is dissolved in solution keep being not more than 0.05 mg/litre.Rotate the stirring vane that is located in the reactor with fixing speed, these solution and gas are evenly mixed.The Ni ion that calculates input reactor by the concentration and the charging rate of the aqueous solution and total input speed of Mn ion are 1.2 * 10
-3
The pH of solution keeps constant basically in reactor, and the oxide particle concentration of metal salt concentrations and generation is when being in stable state basically, and this method is collected the suspended substance that overflows reactor and by the decantation sediment separate out.Washing sediment with water, is metal oxide powder 80 ℃ of dryings 72 hours in atmosphere by the sediment of water-wet.
The metal oxide particle that makes " a " is for spherical, and its average grain diameter is 10 μ m.The ICP emission spectrographic analysis shows the ratio Ni of metallic element in the metallic particles: Mn=9: 1 (atomic ratio).Measure total valence mumber of all metals by iodimetry, and be 3.5 by the average valence mumber that total valence mumber calculates Mn.XRD figure shape shows that nickel oxide is single-phase β-(OH)
2Owing to have correlation (Vegard ' s law) between the average valence mumber of Mn or content and the lattice constant, can affirm that Mn has replaced part Ni.
When stirring metal oxide particle " a " in water, dropping contains 0.09 mol CoSO
4With 0.01 mol NiSO
4Mixed aqueous solution, contain the aqueous solution of 0.23 mol NaOH and contain 0.4 mol NH
3The aqueous solution.This can make the cobalt oxide that contains Ni be deposited on the surface of metal oxide particle " a " gradually.At this moment, in reactor, feed the gaseous state argon, to prevent making cobalt oxidation owing to the oxygen of dissolving.
Then, this method is filtered the suspended substance that contains these particles, washes particle with water, and dry back obtains active material A.The amount of forming the coating that covers particle " a " in the calculated activity materials A by ICP emission spectrographic analysis and particle " a " is formed with it.The ratio C o of metallic element: Ni=9 in the coating: 1 (atomic ratio) is benchmark in hydroxide, and the quantity of coating is 5% (weight).
Embodiment 2
Adopt the method identical with the coating of embodiment 1 preparation active material A to obtain active material B, wherein have the Mn of containing cobalt oxide coating to form on metal oxide particle " a " surface, difference is, by containing 0.09 mol CoSO
4With 0.1 mol MnSO
4Mixed aqueous solution replaced C oSO
4And NiSO
4Mixed aqueous solution.Calculate the ratio C o of metallic element in the coating: Mn=9 according to top mode: 1 (atomic ratio) is benchmark with hydroxide, and the quantity of coating is 7% (weight).
Comparative example
Adopt the method identical with the coating of embodiment 1 preparation active material A to obtain active material X, wherein metal oxide particle " a " has been coated with cobalt oxide, and difference is, by containing 0.1 mol CoSO
4Aqueous solution replaced C oSO
4And NiSO
4Mixed aqueous solution.
By active material A, the B and the X assembled battery that obtain.Method is that at first adding 2 gram yttrium oxide powders and 30 gram water in each 100 gram active material powder are mediated this mixture for sticking with paste.It is in 95% the foaming nickel substrate that this thickener is inserted voidage, dry and extrusion forming.Obtain the nickel cathode plate.This minus plate is cut into pre-sizing, the contact conductor point is welded on the minus plate of predetermined size.Obtain the nickel cathode that theoretical capacity is 1300mAh.The theoretical capacity of nickel electrode is that the Ni of hypothesis in the active material one electron reaction takes place and calculates.
Adopt the known anode that is used for alkaline battery as anode.Use alloy MmNi herein by the absorption hydrogen of following method preparation
3.55Co
0.75Mn
0.4Al
0.3As anode.This method is that the mixture of Mm, Ni, Co, Mn and the Al of mixed melts in arc furnace as requested, obtains the alloy of the absorption hydrogen of required composition.This alloy block of mechanical crushing is the powder of 30 μ m particle diameters in inert atmosphere.Add entry and carboxymethyl cellulose as adhesive in powder, mediating this mixture is thickener.Add to depress this thickener is inserted electrode basement, the positive plate that the hydrogen alloy that is absorbed constitutes.This positive plate is cut into pre-sizing.The capacity of obtaining is the anode of 2000mAh.
This anode and negative electrode are combined to form one group of screw electrode mutually by a dividing plate, and dividing plate is made up of the sulfonation polypropylene nonwoven fabric of 0.15 millimeters thick.Should organize electrode and insert battery container.Inject 2.2 milliliters of electrolyte (9 mol KOH), with the opening of the sealing plate sealed cell shell that safety valve is arranged, the operating pressure of safety valve is about 20kgf/cm
2Obtain the cylindrical seal Ni-metal hydride accumulator of AA size.
The active material X of active material B, comparative example that estimates active material A, the embodiment 2 comprise embodiment 1 respectively according to the methods below is as the performance of each sealed cell of negative electrode.Evaluation method is, each battery is with the current charges of 130mA 18 hours, and to be discharged to 20 ℃ of cell voltages with 260mA be 1.0V.Recharge and discharge cycles.Measure discharge capacity, the relation between the utilance of definite charging and discharge cycles number of times and active material.The utilance of active material is with supposing Ni the ratio calculation of the theoretical capacity of one electron reaction to take place by the actual discharge capacity.
Fig. 1 is the graph of a relation that shows between charge-discharge cycles number of times and the active material utilization.Can be well understood to by this figure, comprise that the utilance of battery of the active material X of comparative example reduces in 300 circulation backs, comprise the active material A of embodiment 1 and 2 and the battery of B, the utilance of active material does not still obviously descend after 400 circulations.
Embodiment 3
This embodiment has changed the mixed proportion of Co salt and Ni salt in the method for coating of active material A of preparation embodiment 1, in the active material that makes in Ni and the coating all metallic elements various ratio arranged.The ratio of all metallic elements that comprise in Ni and the coating changes by 0,0.3,0.5,10,20 and 25% (mole).
Resemble the cylindrical seal battery of embodiment 1 with these active material preparations.Measure the relation between charging and discharge cycles number of times and the active material utilization under the same conditions.
Fig. 2 is the graph of a relation that shows between charge-discharge cycles number of times and the various active material utilization.Can be well understood to by this figure, when Ni content was not less than 0.5% (mole), the utilance of active material did not obviously descend 400 circulation backs.Ni content causes utilance to be lower than initial conditions greater than 20% (mole).This is owing to this fact, and promptly the very big minimizing of Co content has reduced the conductance of coating in the coating.The appropriate level of Ni should be not less than 0.5% (mole) in the coating in other words, and is not more than 20% (mole).
Active material B to embodiment 2 obtains identical result.This shows that the appropriate level of Mn in the coating should be not less than 0.5% (mole), and is not more than 20% (mole).
Although only comprised a kind of among Ni or the Mn in the coating of the foregoing description,, comprised that simultaneously the improvement structure of the coating of Ni and Mn also has identical effect.
In the top embodiment, coating comprises that cobalt hydroxide is as key component.The cobalt oxide layer that obtains by the hydrogen oxide cobalt oxide has identical effect.In this situation, the appropriate level of Ni or Mn also should be not less than 0.5% (mole), and is not more than 20% (mole).
Foaming nickel can be used as the cathode substrate among the top embodiment.Other porous metals substrate, for example three-dimensional porous metallic substrates resembles nickel felt and two-dimentional porous metals substrate, resembles perforated metal, all has identical effect.
As mentioned above, the invention provides the active material of cathode that is used for alkaline battery, it can keep high usage for a long time.So alkaline battery of be improved energy density and cycle performance.
Although described the present invention by the preferred embodiment that proposes, should be appreciated that such disclosure is not construed as limiting.After having read above-mentioned disclosure, those skilled in the art undoubtedly can understand various changes and modification.Therefore, claims have covered all changes and the modification in spirit and scope of the invention.
Claims (7)
1. active material of cathode that is used for alkaline battery, it comprises:
The particle of nickel oxide solid solution or eutectic mixture, it has β-Ni (OH)
2Crystal structure, and contain Mn at least, wherein the average valence mumber of Mn is not less than 3.3; With
In the cobalt oxide solid solution of described particle surface formation or the coating of eutectic mixture, it contains at least a element among Ni and the Mn.
2. the active material of cathode that is used for alkaline battery as claimed in claim 1 is characterized in that in the described coating molar content of at least a element Ni and Mn is not less than 0.5% of all metallic elements in the described coating, and is not more than 20%.
3. the active material of cathode that is used for alkaline battery as claimed in claim 2 is characterized in that the molar content of at least a element Ni and Mn in the described coating is not more than 10% of all metallic elements in the described coating.
4. the active material of cathode that is used for alkaline battery as claimed in claim 1, it is characterized in that being used to being coated with the quantity of the described cobalt oxide of described nickel oxide, with hydroxide is benchmark, and its weight is being not less than 1%, and is not more than in 20% the nickel oxide weight range.
5. the active material of cathode that is used for alkaline battery as claimed in claim 1 is characterized in that described active material of cathode is sphere or the torispherical powder that tap density is not less than 1.7g/cc.
6. negative electrode that is used for alkaline battery, it comprises active material as claimed in claim 1.
7. the negative electrode that is used for alkaline battery as claimed in claim 6 is characterized in that described negative electrode also comprises yttria particles.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP167077/1998 | 1998-06-15 | ||
| JP16707798A JP4252641B2 (en) | 1998-06-15 | 1998-06-15 | Positive electrode for alkaline storage battery and positive electrode active material |
| JP167077/98 | 1998-06-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1239331A true CN1239331A (en) | 1999-12-22 |
| CN1163990C CN1163990C (en) | 2004-08-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991013603A Expired - Fee Related CN1163990C (en) | 1998-06-15 | 1999-01-20 | Cathode active material for alkaline storage battery and cathode using the same |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US6255019B1 (en) |
| EP (1) | EP0967673A3 (en) |
| JP (1) | JP4252641B2 (en) |
| CN (1) | CN1163990C (en) |
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|---|---|---|---|---|
| CN107086296A (en) * | 2016-02-12 | 2017-08-22 | Fdk株式会社 | The positive active material of alkaline secondary cell and the alkaline secondary cell containing the positive active material |
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| CN109713281B (en) * | 2018-12-29 | 2021-12-17 | 蜂巢能源科技有限公司 | Positive electrode material of lithium ion battery and preparation method thereof |
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| KR100373724B1 (en) * | 1995-12-15 | 2003-05-16 | 삼성에스디아이 주식회사 | Cathode and anode electrode plates for alkali storage battery and production thereof |
| JP3533032B2 (en) * | 1996-04-03 | 2004-05-31 | 松下電器産業株式会社 | Alkaline storage battery and its manufacturing method |
| US6042753A (en) * | 1996-10-06 | 2000-03-28 | Matsushita Electric Industrial Co., Ltd. | Active materials for the positive electrode in alkaline storage batteries |
| JP3268989B2 (en) * | 1996-12-11 | 2002-03-25 | 三洋電機株式会社 | Nickel electrode for alkaline storage battery |
| JP3489960B2 (en) * | 1997-04-01 | 2004-01-26 | 松下電器産業株式会社 | Alkaline storage battery |
| US6074785A (en) * | 1997-04-14 | 2000-06-13 | Matsushita Electric Industrial Co., Ltd. | Nickel/metal hydride storage battery |
| US6132639A (en) * | 1998-03-05 | 2000-10-17 | Mitsui Mining & Smelting Company, Ltd. | Manganese-nickel mixed hydroxide for battery active material and process for manufacturing thereof |
-
1998
- 1998-06-15 JP JP16707798A patent/JP4252641B2/en not_active Expired - Fee Related
-
1999
- 1999-01-12 EP EP99100322A patent/EP0967673A3/en not_active Withdrawn
- 1999-01-20 CN CNB991013603A patent/CN1163990C/en not_active Expired - Fee Related
- 1999-03-01 US US09/260,359 patent/US6255019B1/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107086296A (en) * | 2016-02-12 | 2017-08-22 | Fdk株式会社 | The positive active material of alkaline secondary cell and the alkaline secondary cell containing the positive active material |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0967673A2 (en) | 1999-12-29 |
| JP2000003706A (en) | 2000-01-07 |
| US6255019B1 (en) | 2001-07-03 |
| EP0967673A3 (en) | 2001-10-10 |
| JP4252641B2 (en) | 2009-04-08 |
| CN1163990C (en) | 2004-08-25 |
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